JP6371684B2 - Laminated film - Google Patents

Description

  The present invention relates to a laminated film.

  In recent years, in the molding of automotive parts, regulations on harmful substances discharged in the painting and plating process have become more stringent due to environmental problems, and acrylic decorative films and protective films are especially focused on protecting these substitutes and parts. Has been. Since these protective films and decorative films are used by adhering to the surface of the base material, transparency that allows the prints and patterns on the surface of the base material to be clearly seen, and bending resistance during insert and in-mold molding Cracking is required.

  In addition, since the film itself is printed, not only chemical resistance, but also in the vehicle interior and exterior members, there are many opportunities to come into contact with human hands, so the lactic acid components contained in human sebum and sweat, When using sunscreens such as COPATONE (registered trademark) and insecticides in hot areas, there is an increasing number of cases where deterioration of the base material due to adhesion to the inner and outer members becomes a problem, and resistance to contamination. Is also required.

  In order to satisfy these required qualities, a multilayer film in which a fluororesin excellent in weather resistance and chemical resistance and a methacrylic resin composition are coextruded and a surface hard coat treatment with a fluororesin Resin film has a strong interest in the market. Among these, a method of decorating the surface of a plastic molded product as a coating substitute with a film obtained by laminating a vinylidene fluoride resin that can be melt-molded on an acrylic resin as a fluororesin has attracted attention.

  By treating an acrylic resin film with a vinylidene fluoride resin, the stain resistance against lactic acid and the like is improved. However, the vinylidene fluoride resin is a crystalline resin and has high crystallization speed, so it satisfies transparency. It is very difficult. Therefore, film thinning (see Patent Document 1), mixing of vinylidene fluoride resin with methacrylic resin (see Patent Document 2), molding conditions during film processing (extrusion molding temperature, discharge speed, residence time in the extruder) Although studies such as control (see Patent Document 3) have been made, it is not easy to satisfy the required transparency by these methods.

  In addition, with vinylidene fluoride resin, it is difficult to achieve surface hardness that is desired for vehicle member applications.

  Although a surface treatment agent using a fluorine-based acrylic resin or the like (see Patent Documents 4 and 5) is disclosed, this method has stain resistance against lactic acid, but is insufficient in stain resistance against sunscreen and insecticide. . Since this surface treatment agent is premised on coating, it is easy to dissolve in a specific organic solvent, and it is difficult to develop stain resistance to all solvents and chemicals.

  In order to solve such problems (also), a laminated film (Patent Document 6) is disclosed in which a fluorine-based acrylic resin is laminated on at least one side of an acrylic resin film by coextrusion. Although this method improves the stain resistance against solvents and chemicals, there is a problem that the stain resistance against sunscreens and insecticides is not sufficient.

JP-A-57-187248 Japanese Patent Application Laid-Open No. 5-50566 Japanese Patent Laid-Open No. 6-80794 JP 2013-185072 A JP 2014-037511 A JP2011-166861A

  Therefore, the present invention can be used for vehicle interior and exterior member applications, and is excellent in transparency, surface hardness, chemical resistance, lactic acid components contained in human sebum / sweat, sunscreen agents and insecticides. Another object of the present invention is to provide a novel laminated film.

  As a result of intensive studies in view of the above circumstances, the present inventor has found that the fluorine-based acrylic resin layer is laminated on the base film through a base layer containing a resin having a solid content hydroxyl value of 150 or more, thereby achieving transparency. We succeeded in producing a laminated film with excellent surface hardness, chemical resistance, and anti-staining properties against sunscreens and insecticides that could not be achieved with a fluorine-based acrylic resin layer alone.

  The laminated film preferably has a tensile elongation at 120 ° C. of 150% or more.

  The base film is preferably a rubber particle-containing acrylic film.

  The base layer is preferably a layer containing an acrylic resin copolymerized with a hydroxyl group-containing vinyl monomer and another copolymerizable vinyl monomer.

（式中、Ｒ_１は直鎖、枝分かれ鎖状、または環状の炭素数１〜６のアルキレン基、Ｒ_２はＨまたはメチル基である。） The hydroxyl group-containing vinyl monomer is preferably a monomer represented by the general formula (1).

(In the formula, R ₁ is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, and R ₂ is H or a methyl group.)

The fluorine-based acrylic resin layer is preferably a layer containing a resin obtained by copolymerizing a fluorine-containing vinyl monomer and another copolymerizable vinyl monomer.

（式中、Ｒ_１は直接結合、直鎖もしくは枝分かれ鎖状の炭素数１〜７のアルキレン基、または前記アルキレン基上のいずれかのＨがＦに置換されたフッ素置換アルキレン基、Ｒ_２はＨまたはメチル基である。） The fluorine-containing vinyl monomer is preferably a monomer represented by the general formula (2).

(In the formula, R ₁ is a direct bond, straight or branched chain alkylene group having 1 to 7 carbon atoms or a fluorine-substituted alkylene group in which any of the H is substituted with F on the alkylene radical,, R ₂ is H or methyl group.)

  The use of the laminated film is preferably vacuum forming, pressure forming, vacuum / pressure forming, insert forming, or in-mold forming.

  The laminated film of the present invention is excellent in transparency, surface hardness, chemical resistance, and stain resistance.

The laminated film in the present invention is a laminated film containing a resin in which a fluorine-based acrylic resin layer is laminated on a base film through a base layer, and the base layer has a solid content hydroxyl value of 150 or more.
[Base layer]
Although it will not specifically limit if a base layer is a layer containing resin with a solid content hydroxyl value of 150 or more, It is more preferable that it is a layer containing resin with a solid content hydroxyl value of 180 or more.

Here, the solid content hydroxyl value is a numerical value calculated from the formula shown below.
Solid content hydroxyl value = KOH mg / total amount of resin not containing KOH mg: number of moles of hydroxyl group-containing monomer contained in base layer × 56100 × N (N: number of hydroxyl groups per molecule of hydroxyl group-containing monomer)

Moreover, the solid content hydroxyl value of this resin can also be calculated | required by the measuring method of JISK1557-1.

The base layer is preferably a layer containing an acrylic resin obtained by copolymerizing a hydroxyl group-containing vinyl monomer and another copolymerizable vinyl monomer. Furthermore, the hydroxyl group-containing vinyl monomer is preferably a monomer represented by the following general formula (1). If it contains a large number of hydroxyl groups, it will not mix with the oil component, so it is possible to prevent the infiltration of the oil component, and if it is a (meth) acrylate structure, the substrate film is an acrylic substrate film. This is because adhesion with the film becomes possible.

（式中、Ｒ_１は直鎖、枝分かれ鎖状、または環状の炭素数１〜６のアルキレン基、Ｒ_２はＨまたはメチル基である。）

(In the formula, R ₁ is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, and R ₂ is H or a methyl group.)

Known monomers can be used as the monomer represented by the general formula (1). Specific examples thereof include hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 1,4-butanediol monomethacrylate, hydroxy Examples include ethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and 1,4-butanediol monoacrylate. Moreover, the C1-C6 alkylene group which forms acrylic ester may be linear, branched or cyclic. These may be used alone or in combination of two or more.

Among these, transparency when formed into a film-like molded product, adhesion with a base film when the base film is an acrylic resin, chemical resistance, and contamination resistance against lactic acid, sunscreen agents, insecticides, etc. From the viewpoint of properties, hydroxyethyl methacrylate and hydroxypropyl methacrylate which are methacrylate monomers are preferable.

  The monomer represented by the general formula (1) may be copolymerized with other copolymerizable vinyl monomers. Other copolymerizable vinyl monomers include, for example, methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, methacrylic acid-i-propyl, methacrylic acid-n-butyl, methacrylic acid isobutyl, methacrylic acid. -T-butyl, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, adamantyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, etc., methyl acrylate, methyl acrylate, ethyl acrylate, -N-propyl acrylate, isopropyl acrylate, -n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, acrylic acid- 2-ethylhexyl, adamantyl acrylate, dodecyl acrylate, isobornyl acrylate, glycidyl methacrylate, glycidyl acrylate, allyl methacrylate, allyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, Phenyl methacrylate, phenyl acrylate, α-methylstyrene, p-vinyltoluene, methacrylamide, acrylamide, N, N-dimethylmethacrylamide, N, N-dimethylacrylamide, acrylic acid-2,2,6,6-tetra Methyl-4-piperidyl, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl Aliphatic vinyl ether compounds such as ether and cyclohexyl vinyl ether, 2,3-dihydrofuran, 3,4-dihydro-2H-pyran, trimethoxysilylpropyl methacrylate, maleates, fumarates, styrene, acrylonitrile, Methacrylonitrile, 2-hydroxyethyl crotonate, 2-hydroxypropyl crotonate, 3-hydroxypropyl crotonate, 3-hydroxybutyl crotonate, 4-hydroxybutyl crotonate, 5-hydroxypentyl crotonate, 6-crotonate Allyl group-containing compounds such as hydroxyhexyl, allyl alcohol and allyl glycidyl ether, alkyl crotonates such as methyl crotonate, ethyl crotonate and propyl crotonate, vinyl acetate, Aliphatic carboxylic acid vinyl esters such as vinyl pionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl stearate, and cycloaliphatic carboxyl such as vinyl cyclohexanecarboxylate Examples thereof include vinyl acid esters, vinyl benzoates, vinyl cinnamates, and aromatic carboxylic acid vinyl esters such as vinyl tert-butyl benzoate. These may be used alone or in combination of two or more.

  Other copolymerized vinyl monomers are not essential components, and are appropriately selected and used as needed according to the base material, purpose of use, etc. in designing the film.

  Among these, alkyl methacrylate is more preferable from the viewpoints of transparency when formed into a film-like molded article and adhesion to the base film when the base film is an acrylic resin. Among them, methyl methacrylate having 1 to 4 carbon atoms of alkyl group, ethyl methacrylate, methacrylic acid-n-propyl, methacrylic acid-i-propyl, methacrylic acid-n-butyl, methacrylic acid-i-butyl, methacrylic acid. Acid-t-butyl is particularly preferred from the standpoint of chemical resistance and hardness.

  When the total amount of the monomer represented by the general formula (1) and other copolymerizable vinyl monomers is 100 parts by weight, the base layer has a monomer content of 30 to 30 represented by the general formula (1). A layer containing a polymer obtained by polymerizing 90 parts by weight and 10 to 70 parts by weight of another copolymerizable vinyl monomer is preferable. More preferably, it is a layer containing 40 to 80 parts by weight of the monomer represented by the general formula (1) and 20 to 60 parts by weight of other copolymerizable vinyl monomers.

  From the viewpoint of realizing chemical resistance at high temperature and adhesion to the base film when the base film is an acrylic resin, the base layer is composed of the monomer represented by the general formula (1) and a methacrylate-based monomer. It is preferable that it is a layer containing a copolymer with a body. The methacrylate monomer is preferably a methacrylic acid ester having 1 to 4 alkyl chain carbon atoms in the alkyl ester, the glass transition point of the acrylic resin is increased, and the chemical resistance at high temperatures is maintained. Moreover, it is preferable to use the monomer shown by General formula (1) so that it may become resin with a solid content hydroxyl value of 150 or more, More preferably, it is a solid content hydroxyl value of 180 or more. If the solid content hydroxyl value is less than 150, the chemical resistance of the film and the stain resistance against sunscreens and insecticides tend to decrease.

  Although there is no restriction | limiting in particular as number average molecular weight of resin contained in a base layer, 3000-1 million are preferable, 5000-500000 are more preferable, 8000-300000 are further more preferable. If the number average molecular weight is less than 3000, the chemical resistance tends to decrease. If the number average molecular weight exceeds 1,000,000, the viscosity of the resin tends to be high and the handleability tends to be lowered.

  Other resins can be mixed in the base layer as necessary. Examples of other resins include acrylic resins, polyester resins, polyether resins, polyamide resins, and polycarbonate resins.

  The resin contained in the base layer may form a three-dimensional crosslink, but it is preferable that the three-dimensional crosslink is not substantially formed. By substantially not forming a three-dimensional crosslink, molding can be performed near the softening temperature of the resin. Here, the fact that substantially no three-dimensional crosslinking is formed means a chain structure having almost no network structure due to crosslinking.

  The resin contained in the base layer is a methacrylate monomer, a polymerizable monomer containing the monomer represented by the general formula (1), and an oil-soluble resin in an organic solvent in a polymerization vessel having a radical polymerization temperature. It is preferable to perform radical polymerization by dropping a radical polymerization initiator. The reaction temperature during radical polymerization is generally preferably 60 to 150 ° C. If this temperature is less than 60 ° C., the radical polymerization initiator is difficult to decompose and the reaction does not proceed easily. If it exceeds 150 ° C., even if the radical polymerization initiator is decomposed by heat to generate radicals, The lifetime is short and the growth reaction is difficult to proceed effectively. The polymerization time depends on the polymerization temperature and other conditions and cannot be determined in general, but generally about 2 to 6 hours is sufficient.

  Examples of the polymerization initiator used in radical polymerization include t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyneodecanate, t-butyl peroxypivalate, t-hexyl peroxy-2- Organic peroxides such as ethyl hexanoate and methyl ethyl ketone peroxide, or 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionitrile) (AIBN), Preferred examples include azo initiators such as 2,2′-azobis (2-methylbutyronitrile). Of course, it is not limited to these. These radical polymerization initiators may be used alone or in combination of two or more. The polymerization method is not particularly limited, and in addition to radical polymerization, any of cationic polymerization and anionic polymerization can be used. Among these, radical polymerization is preferable from an industrial viewpoint.

  The thickness of the base layer is preferably 1 to 10 μm, more preferably 2 to 8 μm, and further preferably 3 to 6 μm. If the thickness of the base layer is less than 1 μm, the chemical resistance tends to decrease, and if it exceeds 10 μm, lamination by the wet coating method becomes difficult.

  [Fluorine-based acrylic resin layer] The fluorine-based acrylic resin layer refers to a layer containing a (meth) acrylate-based polymer containing a fluoroalkyl group.

The fluorine-based acrylic resin layer is preferably a layer containing an acrylic resin obtained by copolymerizing a fluorine-containing vinyl monomer and another copolymerizable vinyl monomer.

The fluorine-containing vinyl monomer is preferably a monomer represented by the general formula (2). This is because the adhesiveness with the base film is excellent when the base film is an acrylic resin.

（式中、Ｒ_１は直接結合、直鎖もしくは枝分かれ鎖状の炭素数１〜７のアルキレン基、または前記アルキレン基上のいずれかのＨがＦに置換されたフッ素置換アルキレン基、Ｒ_２はＨまたはメチル基である。）

(In the formula, R ₁ is a direct bond, straight or branched chain alkylene group having 1 to 7 carbon atoms or a fluorine-substituted alkylene group in which any of the H is substituted with F on the alkylene radical,, R ₂ is H or methyl group.)

As the monomer represented by the general formula (2), known monomers can be used. Specific examples thereof include trifluoromethyl methacrylate, trifluoroethyl methacrylate, trifluoropropyl methacrylate, trifluorobutyl methacrylate, and trifluoro. Hexyl methacrylate, trifluorooctyl methacrylate, 1,1,1,3,3,3-hexafluoro-2-propyl methacrylate, 1,1,1,3,3,3-hexafluoro-2-propyl methacrylate, 2- (Trifluoromethyl) ethyl methacrylate) or trifluoromethyl acrylate, trifluoroethyl acrylate, trifluoropropyl acrylate, trifluorobutyl acrylate, trifluorohexyl acrylate, trifluoroio Tyl acrylate, 1,1,1,3,3,3-hexafluoro-2-propyl acrylate, 1,1,1,3,3,3-hexafluoro-2-propyl acrylate, 2- (trifluoromethyl) Examples include ethyl acrylate. These may be used alone or in combination of two or more.

  Among these, transparency when formed into a film-like molded product, the resin of the base layer is an acrylic resin, adhesion to the base layer when laminated on the base layer, chemical resistance, lactic acid, sunscreen and insecticide From the viewpoint of stain resistance to the agent and the like, trifluoromethyl methacrylate and trifluoroethyl methacrylate, which are methacrylate monomers having a trifluoromethyl group at the terminal, are preferable. The monomer represented by the general formula (2) may be copolymerized with other copolymerizable monomer species.

  Examples of other polymerizable vinyl monomers that can be polymerized include, for example, methyl methacrylate, ethyl methacrylate, methacrylate-n-propyl, methacrylate-i-propyl, methacrylate-n-butyl, methacrylate-i-butyl. , -T-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, adamantyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, acrylate-n-butyl, acrylate isobutyl, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, acrylic Adamantyl acid, dodecyl acrylate, isobornyl acrylate, glycidyl methacrylate, glycidyl acrylate, allyl methacrylate, allyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, phenyl methacrylate, acrylic Acid phenyl, α-methylstyrene, p-vinyltoluene, methacrylamide, acrylamide, N, N-dimethylmethacrylamide, N, N-dimethylacrylamide, acrylic acid-2,2,6,6-tetramethyl-4-piperidyl , Ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl Aliphatic vinyl ether compounds such as nyl ether, 2,3-dihydrofuran, 3,4-dihydro-2H-pyran, trimethoxysilylpropyl methacrylate, maleic acid esters, fumaric acid esters, styrene, acrylonitrile, methacrylonitrile 2-hydroxyethyl crotonate, 2-hydroxypropyl crotonate, 3-hydroxypropyl crotonate, 3-hydroxybutyl crotonate, 4-hydroxybutyl crotonate, 5-hydroxypentyl crotonate, 6-hydroxyhexyl crotonate, Allyl group-containing compounds such as allyl alcohol and allyl glycidyl ether, alkyl crotonates such as methyl crotonate, ethyl crotonate, propyl crotonate, vinyl acetate, vinyl propionate, vinyl butyrate Aliphatic carboxylic acid vinyl esters such as vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl stearate, alicyclic carboxylic acid vinyl esters such as vinyl cyclohexanecarboxylate, vinyl benzoate And aromatic carboxylic acid vinyl esters such as vinyl cinnamate and vinyl tert-butylbenzoate. These may be used alone or in combination of two or more.

  Other copolymerized vinyl monomers are not essential components, and are appropriately selected and used as needed according to the base material, purpose of use, etc. in designing the film.

  Of these, alkyl ester methacrylate is more preferable from the viewpoint of transparency when formed into a film-like molded article and adhesion of the base layer resin to the acrylic resin when the base layer resin is an acrylic resin. Among them, methyl methacrylate having 1 to 4 carbon atoms of alkyl group, ethyl methacrylate, methacrylate-n-propyl, methacrylate-i-propyl, methacrylate-n-butyl, methacrylate-i-butyl, methacrylate Acid-t-butyl is particularly preferred from the standpoint of chemical resistance and hardness.

  The resin contained in the fluorine-based acrylic resin layer is represented by the general formula (2) when the total of the monomer represented by the general formula (2) and other copolymerizable vinyl monomers is 100 parts by weight. A polymer obtained by polymerizing 50 to 100 parts by weight of the monomer shown and 0 to 50 parts by weight of another copolymerizable vinyl monomer is preferable. More preferably, they are 70-99 weight part of monomers shown by General formula (2), and 1-30 weight part of other copolymerizable vinyl monomers. If the monomer represented by the general formula (2) is less than 50 parts by weight, the water repellency and chemical resistance of the film and the stain resistance against sunscreens and insecticides tend to decrease.

  The resin contained in the fluorine-based acrylic resin layer is a copolymer of a monomer represented by the general formula (2) and a methacrylate-based monomer from the viewpoint of realizing heat decomposition resistance and water repellency at high temperatures. preferable.

  When the total of the monomer represented by the general formula (2) and the methacrylate monomer is 100 parts by weight, the monomer represented by the general formula (2) is 50 to 100 parts by weight and the methacrylate single monomer. The polymer is preferably a polymer obtained by polymerizing 50 to 0 parts by weight of the body. More preferably, they are 70-99 weight part of monomers shown by General formula (2), and 1-30 weight part of methacrylate monomers.

  The methacrylate monomer preferably contains 0 to 50 parts by weight, more preferably 1 to 30 parts by weight of a methacrylic acid ester having 1 to 4 alkyl chain carbon atoms in the alkyl ester, The glass transition point of the fluorinated acrylic resin is increased, the water repellency at high temperature is maintained, and the lactic acid resistance is excellent.

  Although there is no restriction | limiting in particular as a number average molecular weight of resin contained in a fluorine-type acrylic resin layer, 3000-1 million are preferable, 5000-500000 are more preferable, 8000-300000 are further more preferable. If the number average molecular weight is less than 3000, the chemical resistance tends to decrease. If the number average molecular weight exceeds 1,000,000, the viscosity of the resin tends to be high and the handleability tends to be lowered.

  If necessary, other resins can be mixed in the fluorine-based acrylic resin layer. Examples of other resins include fluorine resins such as acrylic resin, vinylidene fluoride resin (PVDF), and vinyl fluoride resin (PVF).

  Although the resin contained in the fluorine-based acrylic resin layer may form a three-dimensional crosslink, it is preferable that the three-dimensional crosslink is not substantially formed. By substantially not forming a three-dimensional crosslink, molding can be performed near the softening temperature of the resin. Here, the fact that substantially no three-dimensional crosslinking is formed means a chain structure having almost no network structure due to crosslinking.

  Moreover, it is preferable that the glass transition point of a fluorine-type acrylic resin is 60 degreeC or more. More preferably, it is 70 degreeC or more, More preferably, it is 80 degreeC or more. This is because the car interior temperature in the summer is in such a high temperature state, and a glass transition point higher than this temperature is advantageous for maintaining the contamination resistance.

  The fluorine-based acrylic resin may be copolymerized with an ultraviolet absorber represented by the general formula (3) from the viewpoint of ultraviolet shielding performance, ultraviolet shielding performance retention, and difficulty in bleeding during molding.

(式中、ＸはＨまたはハロゲン、Ｒ₁はＨ、メチルまたは炭素数４〜６のｔ−アルキル基、Ｒ₂は直鎖または枝分かれ鎖状の炭素数２〜１０のアルキレン基、Ｒ₃はＨまたはメチル基である。)

(Wherein X is H or halogen, R ₁ is H, methyl or a t-alkyl group having 4 to 6 carbon atoms, R ₂ is a linear or branched alkylene group having 2 to 10 carbon atoms, R ₃ is H or methyl group.)

  As an ultraviolet absorber shown by General formula (3), what is mentioned by the acrylic resin mentioned later can be applied similarly, and the following are mentioned.

  Examples of the ultraviolet absorber represented by the general formula (3) include 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazoles, and 2- (2′-hydroxy- 5′-acryloyloxyethylphenyl) -2H-benzotriazol, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazol, 2- (2′-hydroxy-5′-methacryloyl) Oxyethylphenyl) -5-chloro-2H-benzotriazol, 2- (2′-hydroxy-5′-methacryloyloxypropylphenyl) -2H-benzotriazol, 2- (2′-hydroxy-5′-methacryloyl) And oxyethyl-3′-t-butylphenyl) 12H-benzotriazole. Among these, 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole is preferable from the viewpoint of cost and handleability.

  The production method of the fluorinated acrylic resin is not particularly limited as long as it is a generally used method, and is a known emulsion polymerization method, emulsion-suspension polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method or Dispersion polymerization is applicable. The fluorine-based acrylic resin is preferably produced by solution polymerization from the viewpoint of the high hydrophilicity of the monomer and the ease of post-treatment. The fluorine-based acrylic resin is preferably produced by suspension polymerization from the viewpoint of the high hydrophobicity of the monomer and the ease of post-treatment.

  The fluorinated acrylic resin is a polymerizable monomer containing a monomer represented by the general formula (2) and other copolymerizable vinyl monomers, a dispersion stabilizer, a dispersion stabilizer, an oil-soluble radical polymerization. It is preferable to carry out the polymerization under stirring for charging an initiator and ion-exchanged water in a polymerization vessel to give shear necessary for preventing coalescence. The other copolymerizable vinyl monomer is preferably a methacrylate monomer.

  Examples of the dispersion stabilizer include gelatin, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyethylene glycol, polyethylene oxide, polyoxyethylene-polyoxypropylene block copolymer, polyacrylamide, polyacrylic acid, and sodium polyacrylate. Examples thereof include polyacrylic acid salts of sodium, sodium alginate such as sodium alginate, water-soluble polymers such as polyvinyl alcohol or partially saponified polyvinyl alcohol, and inorganic substances such as tricalcium phosphate, titanium oxide, calcium carbonate, and silicon dioxide. Of these dispersion stabilizers, polyvinyl alcohol, partially saponified polyvinyl alcohol, hydroxypropyl cellulose, and tricalcium phosphate are particularly preferably used. These dispersion stabilizers may be used alone or in combination of two or more. The amount of the dispersion stabilizer used is, for example, 0.1 to 60 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymerizable monomer. From the viewpoint of contributing to the above, it is particularly preferably 0.1 to 5 parts by weight.

  A surfactant may be added as a dispersion stabilizing aid. Examples thereof include anionic surfactants such as sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, sodium lauryl sulfate, and nonionic surfactants such as polyethylene glycol nonylphenyl ether. These surfactants may be used alone or in combination of two or more. The amount of the dispersion stabilizing aid used is, for example, 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the polymerizable monomer.

  Examples of radical polymerization initiators include organic peroxides such as benzoyl peroxide, o-methoxybenzoyl peroxide, o-chlorobenzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, and 2,2′-azobisisobutyrate. Ronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- (2-propenyl) -2 -Methylpropionamide, 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2'-azo (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis (1-imino-1-pyrrolidino-2- Examples thereof include azo compounds such as methylpropane) dihydrochloride. Among these radical polymerization initiators, ten-hour half-life temperatures of benzoyl peroxide, lauroyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), etc. However, those which are moderately easy to handle compared to others are preferably used. These radical polymerization initiators may be used alone or in combination of two or more.

  The amount of the radical polymerization initiator used is, for example, 0.1 to 5 parts by weight, preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polymerizable monomer. From the viewpoint of contributing to transparency, 0.1 to 1 part by weight is more preferable. The oil-soluble radical polymerization initiator is preferably dissolved in advance in the polymerizable monomer.

  If necessary, for example, sodium nitrite may be added as a water phase polymerization inhibitor.

  As a method for producing polymer particles by suspension polymerization, prior to the start of the reaction, a monomer mixture is mixed with a mixture of a polymerizable monomer, a dispersion stabilizer, an oil-soluble radical polymerization initiator and ion-exchanged water by a shearing force by stirring. A method of adjusting oil droplets to a desired size is preferred.

  In this case, in order to form fine monomer oil droplets of 30 μm or less, it is preferable to use various dispersing means such as a homomixer, a homodisper, a homogenizer, and a line mixer. The size of the monomer oil droplets can be controlled by adjusting the shearing force according to the rotational speed of the dispersing means.

  The monomer oil droplets (polymerizable monomer dispersion) thus prepared are heated to the 10-hour half-life temperature of a normal radical polymerization initiator, and a polymer particle suspension is obtained by conducting a polymerization reaction. . For example, when lauroyl peroxide is used as a radical initiator, the temperature is raised to 55 ° C. or higher, and when 2,2′-azobisisobutyronitrile is used, the temperature is raised to 65 ° C. or higher to perform radical polymerization.

  The fluorine-containing alkyl (meth) acrylate polymer component obtained by polymerization is used as a powder (fine particles) after being subjected to various post-treatment operation processes such as dehydration operation and, if necessary, salting out, from the polymerization reaction solution. .

  The resulting fluoroacrylic resin fine particles preferably have an average particle size of 0.5 to 200 μm, more preferably 1 to 100 μm.

  The average particle diameter of the fine particles is a value measured using a light scattering method in a latex or slurry state using a Microtrac particle size distribution measuring device MT3000 manufactured by Nikkiso Co., Ltd.

  The shape of the fine particles of the fluorinated acrylic resin is not particularly limited, but is preferably a sphere or a spheroid.

  The thickness of the fluorine-based acrylic resin layer is preferably 1 to 10 μm, more preferably 1 to 8 μm, and further preferably 2 to 6 μm. If the thickness of the base layer is less than 1 μm, the chemical resistance tends to decrease, and if it exceeds 10 μm, lamination by the wet coating method becomes difficult.

[Base film]
Although a base film is not specifically limited, It is preferable that it is an acrylic resin. Taking advantage of the excellent properties of acrylic resin, transparency, surface hardness, chemical resistance, especially anti-contamination of chemical products commonly used by humans, such as lactic acid component system derived from human contact, sunscreen and insecticide The balance which was excellent in property can be played. Furthermore, the base film is preferably a rubber particle-containing acrylic resin. This is because it is preferable in terms of bending crack resistance, bending whitening resistance, and thermoformability. Examples of such rubber particles include core-shell type rubber particles having a specific particle diameter and a crosslinking density of rubber particles as disclosed in JP-A-2003-73520, or Japanese Patent Publication No. 55-27576 and patents. As shown in No. 3563166, core-shell type rubber particles having a hard-soft-hard multi-layer structure containing hard cross-linked acrylic particles inside the cross-linked rubber particles and having an excellent balance between transparency and crack resistance. Can be mentioned.

  As the acrylic resin for the base film, a known acrylic resin can be used. In particular, from the viewpoint of hardness and moldability, it is preferable to include a polymer formed by polymerizing 50 to 100 parts by weight of methyl methacrylate and 0 to 50 parts by weight of other copolymerizable monomers. . As other monomers, the same monomers as those of other copolymerizable vinyl monomers used in (C-1b) described later can be preferably used. For example, what is used for the following acrylic ester-based cross-linked elastic body, or alkyl acrylate having 1 to 12 carbon atoms in the alkyl group can be used. Specific examples include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and the like. These monomers may be used independently and may use 2 or more types together.

  The acrylic resin of the base film is preferably an acrylic resin composition containing an acrylic elastic body graft copolymer because it is excellent in resistance to bending cracking and resistance to bending whitening.

  For example, the acrylic resin of the base film is obtained by mixing an acrylic elastic graft copolymer obtained by polymerization and a methacrylic polymer in the form of latex or powder, beads, pellets, etc. Can be used.

  As the acrylic resin of the base film, it is also possible to use a methacrylic polymer produced after an acrylic elastic graft copolymer is produced using the same reactor.

  As an acrylic elastic graft copolymer, a methacrylic ester is copolymerized or a methacrylic ester and a copolymer in the presence of an acrylic ester cross-linked elastic body (cross-linked elastic body mainly composed of an acrylic ester). What is obtained by copolymerizing the monomer mixture (c-1b) which consists of other possible vinyl monomers is preferable.

  Acrylic ester-based cross-linked elastomers include acrylic esters, other vinyl monomers that can be copolymerized as required, and many polymers having two or more non-conjugated double bonds per copolymerizable molecule. What polymerized the monomer mixture (c-1a) which consists of a functional monomer can be used preferably. Monomers and polyfunctional monomers may all be mixed (one-stage polymerization) and used more than once (two-stage polymerization) by changing the composition of the monomer and polyfunctional monomer. The polymerization may be used separately.

  As the acrylate ester in the acrylate ester-based crosslinked elastic body, an alkyl acrylate ester is preferable from the viewpoint of polymerizability and cost, and an alkyl group having 1 to 12 carbon atoms can be used. Specific examples of preferable monomers include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and the like. These may be used alone or in combination of two or more.

  The amount of acrylate ester in the acrylate ester-based crosslinked elastic body is preferably 50 to 99.9% by weight, more preferably 70 to 99.9% by weight in 100% by weight of the monomer mixture (c-1a), and 80 to 99.9% by weight is most preferred. When the amount of the acrylate ester is less than 50% by weight, the impact resistance is lowered, the elongation at the time of tensile break is lowered, and cracks tend to be generated at the time of film cutting. When the amount of acrylic ester is 100% by weight, the monomer mixture (c-1b) is not copolymerized and the hard graft layer tends to be hardly formed.

  Examples of other copolymerizable vinyl monomers in the acrylic ester-based crosslinked elastomer include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate Methacrylic acid alkyl esters such as those having 1 to 12 carbon atoms in the alkyl group (which may be linear or branched), vinyl halides such as vinyl chloride and vinyl bromide, acrylonitrile, methacrylonitrile, etc. Vinyl cyanide, vinyl formate, vinyl acetate, vinyl propionate, etc., aromatic vinyl derivatives such as styrene, vinyltoluene, α-methylstyrene, vinylidene halides such as vinylidene chloride, vinylidene fluoride, acrylic acid, Sodium acrylate, calcium acrylate Acrylic acid and its salts, β-hydroxyethyl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, acrylamide, N-methylol acrylamide and other alkyl ester derivatives, methacrylic acid, sodium methacrylate, methacrylic acid Methacrylic acid such as calcium and salts thereof, methacrylamide, β-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid alkyl ester derivatives such as glycidyl methacrylate, acids such as maleic anhydride, N-alkylmaleimide, phenylmaleimide And anhydride derivatives. These may be used alone or in combination of two or more. Among these, methacrylic acid esters are particularly preferable from the viewpoint of weather resistance and transparency.

  The amount of the other copolymerizable vinyl monomer in the acrylic ester-based crosslinked elastic body is preferably 0 to 49.9% by weight, preferably 0 to 30% by weight, based on 100% by weight of the monomer mixture (c-1a). Is more preferable, and 0 to 20% by weight is most preferable. When the amount of the other vinyl monomer exceeds 49.9% by weight, the impact resistance is lowered, the elongation at the time of tensile break is lowered, and cracks are likely to be generated at the time of film cutting.

  The polyfunctional monomer having two or more non-conjugated double bonds per molecule that can be copolymerized in the acrylic ester-based crosslinked elastomer may be a commonly used monomer such as allyl methacrylate or allyl acrylate. , Triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl malate, divinyl adipate, divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetromethylolmethane tetramethacrylate, Dipropylene glycol dimethacrylate and acrylates thereof can be used. These polyfunctional monomers may be used alone or in combination of two or more.

  The amount of the polyfunctional monomer having two or more non-conjugated double bonds per molecule that can be copolymerized in the acrylate cross-linked elastomer is determined by the stress along with the average particle size of the acrylate cross-linked elastomer. It greatly affects whitening, elongation at the time of tensile break, or transparency.

  The blending amount of the polyfunctional monomer in the acrylic ester-based crosslinked elastic body of the present invention is preferably 0.1 to 10% by weight, and 1.0 to 4 in 100% by weight of the monomer mixture (c-1a). Weight percent is more preferred. When the blending amount of the polyfunctional monomer is 0.1 to 10% by weight, it is preferable from the viewpoint of bending cracking resistance, bending whitening resistance, and resin flowability during molding. When the blending amount of the polyfunctional monomer is 10% by weight or more, the bending resistance and the transparency of the film may be lowered.

  In the presence of an acrylic ester-based cross-linked elastic body (cross-linked elastic body mainly composed of an acrylate ester), an acrylic elastic-body graft copolymer contains 50 to 100% by weight of a methacrylic ester and other copolymerizable copolymers. What is obtained by copolymerizing a monomer mixture (c-1b) composed of 0 to 50% by weight of a vinyl monomer is preferred. More preferably, in the presence of 5 to 85 parts by weight of an acrylic ester-based crosslinked elastic body, a monomer comprising 50 to 100% by weight of an alkyl methacrylate and 0 to 50% by weight of another copolymerizable vinyl monomer It is obtained by copolymerizing 95 to 15 parts by weight of the body mixture (c-1b) in at least one stage. However, the total amount of the monomer mixture (c-1a) and the monomer mixture (c-1b) shall satisfy 100 parts by weight.

  The blending amount of the methacrylic acid alkyl ester in the monomer mixture (c-1b) is preferably 80% by weight or more, more preferably 85% by weight, and still more preferably 90% by weight in terms of hardness and rigidity. As other copolymerizable vinyl monomers, those used for the acrylate-based crosslinked elastomer and alkyl acrylates having 1 to 12 carbon atoms in the alkyl group can be used. Specific examples include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and the like. These monomers may be used independently and may use 2 or more types together.

  In this case, in the monomer mixture (c-1b) (graft copolymerization composition), a component (free polymer) that becomes an ungrafted polymer is generated without grafting to the acrylate-based crosslinked elastic body. This component (free polymer) can be used as part or all of the methacrylic polymer.

  A part of the acrylic elastic graft copolymer [(c-1a) and grafted (c-1b)] becomes insoluble in methyl ethyl ketone.

  The graft ratio to the acrylic ester-based crosslinked elastic body is preferably 30 to 250%, more preferably 50 to 230%, and still more preferably 70 to 220%. When the graft ratio is less than 30%, the bending whitening resistance is lowered, the transparency is lowered, the elongation at the time of tensile break is lowered, and cracks tend to be generated at the time of film cutting. If it exceeds 250%, the melt viscosity at the time of film formation tends to be high, and the moldability of the film tends to deteriorate.

  The production method of the acrylic elastic graft copolymer is not particularly limited, and a known emulsion polymerization method, emulsion-suspension polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method or dispersion polymerization method can be applied. However, the emulsion polymerization method is particularly preferable from the viewpoint that the adjustment range of the resin structure is large.

  The average particle diameter d of the acrylic elastic body graft copolymer is preferably more than 100 nm and less than or equal to 400 nm, more preferably more than 100 nm and not more than 350 nm, and still more preferably more than 100 nm and not more than 300 nm. When the average particle diameter of the acrylic elastic graft copolymer is 100 nm or less, the impact resistance and bending cracking resistance of the film tend to decrease. If it exceeds 400 nm, the transparency of the film tends to decrease.

  The average particle diameter of the acrylic elastomer graft copolymer here is a value measured using a light scatter method in a latex state using a Microtrac particle size distribution analyzer MT3000 manufactured by Nikkiso Co., Ltd.

  What is the average particle diameter d (nm) of the acrylate-based crosslinked elastic body in the acrylic resin of the base film and the amount w (% by weight) of the polyfunctional monomer used in the acrylate-based crosslinked elastic body? The stress whitening of the film, the elongation at the time of tensile breakage, or the transparency is greatly affected. Therefore, it is preferable that the relational expression: 0.02d ≦ w ≦ 0.06d is satisfied, and 0.02d ≦ w ≦ 0. It is more preferable to satisfy 05d. If the amount of the polyfunctional monomer is within the above range, stress whitening is unlikely to occur, impact resistance is unlikely to decrease, elongation at the time of tensile rupture is unlikely to decrease, cracks are unlikely to occur during film cutting, and transparency is decreased. There is an advantage that the film formability is good.

  The average particle diameter d of the acrylate-based crosslinked elastic body in the acrylic resin of the base film is preferably 50 to 200 nm, more preferably 50 to 160 nm, still more preferably 50 to 120 nm, and particularly preferably 60 to 120 nm. If the average particle diameter d of the acrylic ester-based cross-linked elastic body is 50 nm or more, impact resistance and elongation at the time of tensile break are less likely to be reduced, and cracks are less likely to occur during film cutting. Is preferable, and transparency, particularly transparency after vacuum forming (maintaining transparency before and after heating) can be ensured.

  The average particle diameter d of the acrylic ester-based cross-linked elastic body is adjusted to a accelerating voltage of 80 kV using a transmission electron microscope (JEM 1200EX, manufactured by JEOL Ltd.) after adjusting the sample from the obtained film by a freezing ultrathin section method. It is a value measured based on a photograph observed at 40000 times.

  The reduced viscosity of the methyl ethyl ketone soluble part of the acrylic resin is preferably 0.2 to 0.8 dl / g, preferably 0.2 to 0.8, under the condition that 0.1 g of the polymer is dissolved in 100 ml of chloroform and measured at 25 ° C. 7 dl / g is more preferable, and 0.2 to 0.6 dl / g is more preferable. If it is the said range, the elongation at the time of the tensile fracture of the film obtained does not fall easily, and when a film is cut | disconnected, it is hard to generate | occur | produce a crack. Moreover, it has the advantage that the moldability of a film is favorable.

  Here, the reduced viscosity of methyl ethyl ketone soluble matter is measured by measuring the flow time of solution and solvent in a temperature-controlled room at 25 ° C. using a standard viscosity tube based on ISO1628-1 after dissolving acrylic resin in methyl ethyl ketone. These values are calculated using these values and the solution concentration.

  The acrylic elastomeric graft copolymer, which is obtained by copolymerizing the ultraviolet absorber represented by the general formula (3), has a UV shielding performance, a UV shielding performance retention rate, and is difficult to bleed during molding. preferable.

(式中、ＸはＨまたはハロゲン、Ｒ₁はＨ、メチルまたは炭素数４〜６のｔ−アルキル基、Ｒ₂は直鎖または枝分かれ鎖状の炭素数２〜１０のアルキレン基、Ｒ₃はＨまたはメチル基である。)

(Wherein X is H or halogen, R ₁ is H, methyl or a t-alkyl group having 4 to 6 carbon atoms, R ₂ is a linear or branched alkylene group having 2 to 10 carbon atoms, R ₃ is H or methyl group.)

  Examples of the ultraviolet absorber represented by the general formula (3) include 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazoles, and 2- (2′-hydroxy- 5′-acryloyloxyethylphenyl) -2H-benzotriazol, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazol, 2- (2′-hydroxy-5′-methacryloyl) Oxyethylphenyl) -5-chloro-2H-benzotriazol, 2- (2′-hydroxy-5′-methacryloyloxypropylphenyl) -2H-benzotriazol, 2- (2′-hydroxy-5′-methacryloyl) And oxyethyl-3′-t-butylphenyl) 12H-benzotriazole. Among these, 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole is preferable from the viewpoint of cost and handleability.

  The copolymerization ratio of the ultraviolet absorber represented by the general formula (3) is preferably 0.01 to 30 parts by weight, and 0.01 to 25 parts by weight with respect to 100 parts by weight of the acrylic elastic graft copolymer. More preferably, 0.01-20 weight part is further more preferable, and 0.05-20 weight part is especially preferable. When the copolymerization ratio of the ultraviolet absorber represented by the general formula (3) is less than 0.01 parts by weight, the effect of increasing the weather resistance of the obtained film tends to hardly occur. There is a tendency that the effect of increasing impact resistance and bending cracking resistance hardly occurs.

  The copolymer of the ultraviolet absorber represented by the general formula (3) may be copolymerized in any layer of the acrylic elastomer graft copolymer, but the acrylate ester crosslinked elastomer and the methacrylate ester. The copolymer is preferably copolymerized with the copolymer (c-1b), and the ultraviolet absorber is more preferably uniformly copolymerized with the entire acrylic elastic graft copolymer.

  The method for copolymerizing the ultraviolet absorber represented by the general formula (3) is not particularly limited, and it is preferable to perform copolymerization during the production of the acrylic elastic graft copolymer.

  As an initiator in the polymerization of the acrylic ester-based crosslinked elastic body, known initiators such as organic peroxides, inorganic peroxides, and azo compounds can be used. Specifically, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, succinic acid peroxide, peroxymaleic acid t-butyl ester, cumene hydroperoxide, Organic peroxides such as benzoyl peroxide, sodium formaldehyde sulfoxylate, reducing sugar, ascorbic acid, inorganic peroxides such as potassium persulfate, sodium persulfate, divalent iron salts, and azobisisobutyrate An azo compound such as ronitrile is also used. These may be used alone or in combination of two or more. These initiators are combined with reducing agents such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, hydroxyacetone acid, ferrous sulfate, ferrous sulfate and disodium ethylenediaminetetraacetate It may also be used as a normal redox type initiator.

  Among these, redox combined with inorganic reducing agents such as divalent iron salts and / or organic reducing agents such as formaldehyde sulfoxylate sodium, reducing sugar and ascorbic acid from the viewpoint of polymerization stability and particle size control. It is preferred to use a system initiator.

  The organic peroxide can be added by a known addition method such as a method of adding it as it is to the polymerization system, a method of adding it mixed with a monomer, a method of adding it dispersed in an emulsifier aqueous solution, or the like. From the viewpoint of transparency, a method of adding a mixture to a monomer or a method of adding it by dispersing in an aqueous emulsifier solution is preferable.

  The surfactant used for emulsion polymerization is not particularly limited, and any surfactant for normal emulsion polymerization can be used. For example, anionic surfactants such as sodium alkyl sulfonate, sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, sodium lauryl sulfate, and sodium fatty acid, alkylphenols, aliphatic alcohols and propylene oxide, ethylene oxide Nonionic surfactants such as reaction products are listed. These surfactants may be used alone or in combination of two or more. Furthermore, if necessary, a cationic surfactant such as an alkylamine salt may be used.

  The obtained acrylic elastic graft copolymer latex is separated and recovered by a usual coagulation, washing and drying operation, or by a treatment such as spray-drying or freeze-drying.

  As the methacrylic polymer, a methacrylic acid ester polymer or a copolymer with another vinyl monomer copolymerizable with the methacrylic acid ester can be used. Preferably, a product obtained by copolymerizing a monomer mixture comprising 80 to 100% by weight of a methacrylic acid ester and 0 to 20% by weight of another copolymerizable vinyl monomer can be used.

  From the viewpoint of the hardness and rigidity of the obtained film, the blending amount of the methacrylic acid ester is more preferably 85% by weight or more, and further preferably 90% by weight or more.

  As said methacrylic acid ester, methacrylic acid alkylester is preferable and methyl methacrylate is more preferable at the point which can be obtained easily.

  Examples of other copolymerizable vinyl monomers in the methacrylic polymer include those used for the acrylic elastic graft copolymer. These monomers may be used independently and may use 2 or more types together.

  It is also possible to polymerize the methacrylic polymer separately from the acrylic elastic graft copolymer. In this case, the polymerization method is not particularly limited, and a known emulsion polymerization method, emulsion-suspension polymerization method, suspension polymerization method, bulk polymerization method or solution polymerization method can be applied.

  The average particle diameter of the methacrylic polymer is preferably 100 to 500 μm, and more preferably 100 to 300 μm. If the average particle diameter of the methacrylic polymer is less than 100 μm, impact resistance, bending cracking resistance, and chemical resistance tend to decrease, and if it exceeds 500 μm, transparency tends to decrease.

  The average particle diameter of the methacrylic polymer is a value measured by using a light scattering method in a latex state using a Microtrac particle size distribution measuring device MT3000 manufactured by Nikkiso Co., Ltd.

  As an initiator in the polymerization of a methacrylic polymer, a known organic peroxide, inorganic peroxide, azo, similar to the initiator in the polymerization of an acrylic ester-based crosslinked elastic body (c-1a) described above. Compounds, etc. BR> F initiators can be used. These may be used alone or in combination of two or more.

  The organic peroxide can be added by a known addition method such as a method of adding it to the polymerization system as it is, a method of adding it by mixing with a monomer, a method of adding it by dispersing in an aqueous emulsifier solution, etc. From the viewpoint of properties, a method of adding to a monomer is preferable.

  Examples of the dispersant used for suspension polymerization include dispersants generally used for suspension polymerization, for example, polymer dispersants such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylamide, calcium phosphate, hydroxyapatite, magnesium pyrophosphate, and the like. The slightly water-soluble inorganic salt of In the case of using a hardly water-soluble inorganic salt, it is effective to use an anionic surfactant such as α-olefin sodium sulfonate or sodium dodecylbenzenesulfonate in order to increase dispersion stability. These dispersants may be added one or more times during the polymerization in order to adjust the particle diameter of the resin particles obtained.

  The content of the acrylic ester-based crosslinked elastic body in the acrylic resin is preferably 5 to 100% by weight, more preferably 5 to 45% by weight, and still more preferably 10 to 30% by weight. However, the total amount of acrylic elastic graft copolymer and methacrylic polymer is 100% by weight. If the content of the acrylic elastic graft copolymer is 5% by weight or more, the elongation at the time of tensile break of the obtained film is difficult to decrease, cracks are hardly generated when the film is cut, and stress whitening is not caused. It tends to be difficult to occur. When the content is 5 to 45% by weight, the hardness and rigidity of the obtained film tend to be good.

  The thickness of the base film is preferably 20 to 200 μm, more preferably 30 to 150 μm, and further preferably 40 to 125 μm. When the thickness of the base film layer is less than 20 μm, sufficient transparency and weather resistance cannot be obtained, and the moldability tends to decrease. When the thickness exceeds 200 μm, the cost becomes disadvantageous and the film is wound in a roll shape. Therefore, the handleability tends to be reduced.

[Laminated film]
A film in which a base layer and a fluorine-based acrylic resin layer are laminated on a base film can be manufactured by a general method. Wet coating method, dry laminating method, wet laminating method, hot melt laminating method, heating Examples thereof include a press laminating method, an extrusion laminating method in which a film is melt-extruded with a T die and the like, and a coextrusion method in which the material is melt-bonded outside the die, such as in a die or a multi-slot method. Fluorine-based acrylic resins have poor thermal stability, so there is a stay in melt extrusion where heat history occurs, so thermal decomposition of the resin becomes a critical issue in long-term production. Most preferred is a wet coating method that does not generate odor.
For example, specifically, fluorine-containing alkyl (meth) acrylate-based polymers are easily decomposed by heat, and die lines are frequently generated due to foaming and generation of gel (unmelted material). Therefore, it is preferable to make a fluorine-containing alkyl (meth) acrylate polymer or the like into a solution and to laminate the solution on the base film by a wet coating method.

  Wet coating methods include flow coating method, spray coating method, bar coating method, gravure coating method, gravure reverse coating method, kiss reverse coating method, micro gravure coating method, roll coating method, blade coating method, rod coating method, roll Known coating methods such as a doctor coating method, an air knife coating method, a comma roll coating method, a reverse roll coating method, a transfer roll coating method, a kiss roll coating method, a curtain coating method, a die coating method, and a dipping coating method may be mentioned. Particularly preferred is a vacuum die coater. The vacuum die coater has less coating liquid retention and can increase the air gap.

  The laminated film of the present invention is formed by laminating a base layer and a fluorine-based acrylic resin layer on at least one surface of a base film. The laminated film of the present invention has a beautiful appearance by laminating the base layer and the fluorine-based acrylic resin layer on the base film by a wet coating method that does not cause thermal decomposition of the resin, thereby eliminating foaming and die lines. , Stable production becomes possible.

When laminating by the wet coating method, it is preferable to use solution polymerization or the like in an organic solvent for the production of each resin.
The organic solvent is not particularly limited as long as it can dissolve each component, but the polymerization of the fluorine-based acrylic resin uses a highly polar alcohol-based organic solvent or an organic solvent other than water. The base layer resin is preferably polymerized with a small amount of an alcohol-based organic solvent. Moreover, it is preferable to select so that the organic solvent does not remain after drying in the wet coating method. For example, aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform and carbon tetrachloride, methanol, ethanol Alcohols such as n-propyl alcohol, isopropyl alcohol and n-butyl alcohol, ethers such as dibutyl ether, tetrahydrofuran and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate and n acetate And esters such as -propyl and n-butyl acetate. These solvents may be used alone or in combination of two or more.

  It is desirable to adjust the blending number of the organic solvent to an appropriate coating viscosity. For example, in the case of gravure coating, 20 to 300 mPa · s is preferable, and in the case of die coating, the number of blended parts of the machine solvent having a viscosity of 100 to 3000 mPa · s is preferable.

  The laminated film of the present invention preferably has an overall thickness of 30 to 300 μm, more preferably 30 to 200 μm. If the total thickness of the laminated film is less than 30 μm, the film forming processability tends to be reduced, and wrinkles tend to occur when the film is wound. If it exceeds 300 μm, the transparency of the film is lowered, and further secondary processing is performed. Tend to decrease.

  The laminated film of the present invention preferably has a 120 ° C. tensile elongation of 100% (2.0 times) or more, more preferably 150% (2.5 times) or more, and 200% (3.0 times) or more. Further preferred. If the 120 ° C. tensile elongation is less than 100%, cracks tend to occur frequently during molding (for example, insert molding, in-mold molding). In particular, if the 120 ° C. tensile elongation is 150% or more, it can be stably molded without cracking during molding. 120 ° C. is a temperature at which the laminated film can be heat-softened and processed.

  The laminated film of the present invention is obtained by laminating a fluorine-based acrylic resin layer on a base film via a base layer. In addition, the laminated film has transparency, surface hardness, chemical resistance, and contamination resistance against lactic acid components and sunscreens and insecticides contained in human sebum and sweat, which could not be realized with a fluorine-based acrylic resin layer alone. Can play. Moreover, it is applicable also to a thermoforming use, for example, it can apply to the automotive interior / exterior member which undergoes vacuum forming, pressure forming, vacuum / pressure forming, insert, in-mold forming.

  Here, vacuum / pressure forming is a molding method in which a laminated film is heated and softened, a vacuum is applied between the mold and the laminated film, and then the laminated film is brought into close contact with the mold by compressed air pressure.

  In the present invention, a suitable adhesive or an adhesive layer using an adhesive resin may be provided between the base film layer and the base layer for lamination within a range not impairing the effects of the present invention. .

  Known adhesives and adhesive resins can be used, such as (meth) acrylic acid alkyl ester resins, or copolymers thereof, styrene-butadiene copolymers, polyisoprene rubber, polyisobutylene rubber, etc. Fluorine (meth) containing rubber, polyvinyl ether, silicone, maleimide, cyanoacrylate, vinylidene halide resins such as vinylidene chloride and vinylidene fluoride, and fluorine-containing alkyl (meth) acrylate polymer components Examples thereof include acrylic resins and mixtures with (meth) acrylic acid alkyl ester resins. From the viewpoint of weather resistance and transparency, a (meth) acrylic acid alkyl ester-based resin which is a copolymer mainly composed of a (meth) acrylic acid alkyl ester monomer is preferable. These may be used alone or in combination with a crosslinking agent or a tackifier.

  The (meth) acrylic acid alkyl ester resin is an alkyl ester of acrylic acid or methacrylic acid, and is not particularly limited. For example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-acrylate Butyl, isobutyl acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, etc. Is mentioned.

  As a method for providing the adhesive layer, a method similar to the method for providing the base layer and the fluorine-based acrylic resin layer can be used.

  The laminated film of the present invention preferably has a haze of 2.0 or less, more preferably 1.5 or less, from the viewpoint of appearance when used for an automobile interior / exterior member.

  The haze here is a value measured at a thickness of 75 μm under the conditions of a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 5% in accordance with JIS K6714.

  Applications of the laminated film of the present invention include vehicle applications and building material applications. Specific examples include instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards and other automotive interior applications, weather strips, bumpers, bumper guards, side mud guards, body panels, Spoilers, front rills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts and other automotive exterior applications, AV equipment and furniture products Applications such as front panels, buttons, emblems, surface cosmetics, housings for mobile phones, display windows, buttons, etc., and furniture exterior materials, walls Architectural interior materials such as ceilings and floors, exterior walls such as siding, exterior exterior materials for buildings such as fences, roofs, gates, and windbreak boards, surface decorative materials for furniture such as window frames, doors, handrail sills, and duck It can be used for optical members such as various displays, lenses, mirrors, goggles and window glass, or for interior and exterior applications of various vehicles other than automobiles such as trains, airplanes and ships.

  Among the above-mentioned applications, particularly when laminating on a vehicle interior / exterior member, the surface of the laminated member is preferably a fluorine-based acrylic resin layer, and the adhesive layer with the member is preferably a base layer, and the laminating method is particularly limited. However, a film-in method similar to that described in JP-B-63-6339, JP-B-4-9647, JP-A-7-9484, JP-A-8-323934, JP-A-10-279766, etc. It is preferable to manufacture by a molding method or a film insert molding method. That is, a film that has been given a shape by vacuum forming or the like, or a film that has not been given, is inserted between injection molds, the mold is closed with the film sandwiched, and the base resin is injection-molded. It is preferable to melt and integrate the film on the surface of the injected base resin molded body. At that time, the injection conditions such as the resin temperature and the injection pressure are appropriately set in consideration of the type of the base resin.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples.

  In the following production examples, examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  In addition, each measuring method of the physical property measured in the following Examples and Comparative Examples is as follows.

(Measurement method of solid content hydroxyl value)
The solid content hydroxyl value is a numerical value calculated from the formula shown below.
Solid content hydroxyl value = KOH mg / total amount of resin not containing solvent Here, KOH mg is defined as follows.
KOHmg = number of moles of hydroxyl group-containing monomer × 56100 × N
N represents the number of hydroxyl groups per molecule of hydroxyl group-containing monomer.

  The measurement method of the solid content hydroxyl value will be specifically described below by taking the case of Production Example 4 as an example.

  As for the number of moles of the hydroxyl group-containing vinyl monomer, the number of moles of hydroxyethyl methacrylate used was 0.52 mole (67 g / molecular weight 130), and the number of hydroxyl groups was 1, so KOHmg was 28913 (0.52 × 56100). X1). The total amount of resin without solvent was 101.6 g, assuming that the monomers and initiator used were all incorporated into the resin. Therefore, the solid content hydroxyl value is 285 (28913 / 101.6).

Moreover, the solid content hydroxyl value of this resin can also be calculated | required by the measuring method of JISK1557-1.

(Method for measuring particle diameter of acrylic ester-based crosslinked elastic body)
The obtained film was photographed with a transmission electron microscope (JEM-1200EX, manufactured by JEOL Ltd.) with an acceleration voltage of 80 kV and a RuO ₄ stained ultrathin section method. From the obtained photograph, an acrylate-based crosslinked elastic particle image 100 were randomly selected, and the average value of their particle sizes was determined.

(Method for measuring particle diameter of fluorine-based acrylic resin and acrylic elastic graft copolymer)
Using a Microtrac particle size distribution analyzer MT3000 manufactured by Nikkiso Co., Ltd., measurement was performed using a light scattering method in a latex state. When the resin was prepared by suspension polymerization, it was measured in a slurry state using a Microtrac particle size distribution meter 9210SRA / 9220FRA manufactured by Nikkiso Co., Ltd.

(Evaluation of transparency)
For the transparency of the obtained film, the haze was measured under the conditions of a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 5% in accordance with JIS K 6714.

(Evaluation of chemical resistance)
<Xylene resistance>
One drop (0.02 g) of xylene was dropped on the obtained film, and the change of the film was visually evaluated.
○: No change is observed at all.
(Triangle | delta): A fine dripping trace is recognized.
X: The surface is severely deteriorated, and dripping marks are clearly recognized.

(Evaluation of contamination resistance)
<Evaluation of lactic acid resistance>
A drop of a 10% aqueous lactic acid solution was dropped on the obtained film, allowed to stand at 80 ° C. for 24 hours, then washed with water, and the change in the film was visually evaluated.
○: No change is observed at all.
Δ: Minute pinhole-like dissolution traces are observed.
X: The surface is severely deteriorated and the dissolution mark is clearly recognized.

<DOP resistance>
Two pieces of gauze dipped in DOP (dioctyl phthalate) were placed on the obtained film, left as it was for 72 hours at 80 ° C., then the adhered DOP was wiped off with gauze, the film was washed with water, and the change in the coated part was visually observed. Observed.
○: No change is observed.
(Triangle | delta): A fine coating trace is recognized.
X: The surface is severely deteriorated, and the application mark is clearly recognized.

<Sunscreen resistance [copatotone (registered trademark)]>
One drop (0.005 g) of sunscreen agent (copatone water babes lotion SPF50) was dropped on the obtained film, and it was extended with a brush in the range of 2 × 3 cm. After standing at 80 ° C. for 1 hour, or after standing at 80 ° C., 90 ° C., and 105 ° C. for 24 hours, the attached sunscreen was wiped off with gauze, the film was washed with water, and changes in the coated part were observed visually.
○: No change is observed.
(Triangle | delta): A fine coating trace is recognized.
X: The surface is severely deteriorated, and the application mark is clearly recognized.

<Insecticide resistance>
An insecticide test solution (EcylMethoxycinnamate, Octocrylene, Homosalate, DEET mixed solvent (weight ratio) mixed solvent) is dropped on at least three places on the obtained film, and 23 ° C, 50 ° C, 60 ° C, 74 ° C. After leaving at 1 ° C. for 1 hour or after leaving at 80 ° C. for 24 hours, the adhering mixed solvent was washed with a neutral detergent / water, wiped off with gauze, and changes in the coated part were observed visually.
○: No change is observed.
(Triangle | delta): A fine coating trace is recognized.
X: The surface is severely deteriorated, and the application mark is clearly recognized.

(Measurement method of 120 ° C tensile elongation)
Autograph AGS10KNG (manufactured by Shimadzu Corporation), TERMOSATATIC CHAMBER is Model: TCRI-200SP (manufactured by Shimadzu Corporation), sample size is 10 × 100 mm, chuck is 50 mm, pulling speed is 200 mm / min, A tensile test was performed under the condition of a tensile constant temperature of 120 ° C., and the elongation until cracks occurred in the film was measured.

(Evaluation of bending crack resistance)
The obtained film was bent once by 180 degrees, and the change in the bent portion was visually evaluated.
○: No cracks are observed.
Δ: Slight cracking occurs.
X: The film is broken and completely broken.

(Evaluation of bending whitening resistance)
The obtained film was bent once by 180 degrees, and the change in the bent portion was visually evaluated.
○: Whitening is not recognized.
Δ: Slight whitening is observed when light is transmitted.
X: Whitening is recognized.

(Evaluation of surface hardness)
The surface hardness of the obtained film was evaluated by measuring the pencil hardness according to JIS K5600-5-4.

(Evaluation of adhesion)
The adhesion was evaluated by a cross cellophane tape peeling test of JIS K 5400 (100 mm test at 2 mm intervals).

(Evaluation of film productivity)
<Evaluation of laminated film continuous productivity: (Evaluation Method 1)>
The wet coating method of the laminated film was continuously performed for 2 hours, the operation state was observed, and evaluation was performed according to the following criteria. In the wet coating method, a coating solution prepared by dissolving a hydroxyl group-containing acrylic resin in a mixed solvent of methyl isobutyl ketone and methyl ethyl ketone on a base film is wet coated using a specific bar coater, and then dried at 80 ° C. for 2 minutes. Carried out. Further, a coating solution in which a fluorine-based (meth) acrylic resin was dissolved in a mixed solvent of methyl isobutyl ketone and methyl ethyl ketone was sequentially wet coated using a specific bar coater, and then dried and passed at 80 ° C. for 2 minutes.
○: The film can be produced without causing appearance defects such as firing and streaks (die lines).
X: The film cannot be produced because of appearance defects such as firing and streaks (die lines).

<Evaluation of laminated film continuous productivity: (Evaluation method 2)>
The laminated film was melt-coextruded continuously for 2 hours, its operating condition was observed, and evaluation was performed according to the following criteria. As T-die used for coextrusion, 3 types 3 layer T-die (feed block system) was used. As a resin-side extruder serving as a base film, a 40 mmφ single-screw extruder was used and melt-kneaded at a cylinder set temperature of 200 to 260 ° C. at a discharge rate of 5 to 15 kg / hr. On the other hand, a hydroxyl group-containing acrylic resin and As the extruder on the fluorine-based acrylic resin side, 32 mmφ single screw extruders were used, melt kneading at a cylinder set temperature of 180 to 240 ° C. and a discharge rate of 0.5 to 3 kg / hr, and setting a die temperature of 240 ° C. The molten resin was put into the die thus obtained, and melt co-extrusion molding of the laminated film was performed.
○: The film can be produced without causing appearance defects such as firing and streaks (die lines).
X: The film cannot be produced because of appearance defects such as firing and streaks (die lines).

(Number average molecular weight of resin)
Using HLC8220GPC (manufactured by Tosoh Corporation), connecting three TSKgel Super H5000, H4000, and H3000 (manufactured by Tosoh Corporation) as GPC columns, using THF (with stabilizer) as a solvent, in terms of polystyrene It was measured. Other conditions are measurement temperature: INLET OVEN 40 ° C., sample amount: 10 μl, liquid amount: 0.6 ml / min, detector: RI.

(Production Example 1)
<Fluorine-based acrylic resin (A-1)>
In a dispersion container, 300 parts of deionized water and 1 part of polyvinyl alcohol were added. Separately, 90 parts of 2,2,2-trifluoroethyl methacrylate, 10 parts of methyl methacrylate, 0.5 part of 2,2′-azobis (2-methylbutyronitrile) and 0.06 of 2-ethylhexylthioglycol A monomer solution consisting of parts was prepared and added to the dispersion container. The obtained mixed liquid was subjected to dispersion treatment using a homomixer to obtain a dispersion liquid having a droplet diameter adjusted to 100 nm.

  This dispersion was poured into an 8 L polymerization reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet, and polymerized for 3 hours at a liquid temperature of 80 to 90 ° C. while stirring at 70 ° C. under a nitrogen stream. Reaction was performed.

  By filtering, washing, and drying the obtained dispersion of polymer particles, spherical organic fine particle powder of poly (2,2,2-trifluoroethyl methacrylate) (average) as the fluorinated acrylic resin (a-1) A particle diameter of 100 μm) was obtained.

  Using 100 parts of the obtained fluorinated acrylic resin (a-1) and using a 40 mmφ single screw extruder (manufactured by Osaka Seiki Co., Ltd.) whose temperature was adjusted to 200 ° C., screw rotation speed 75 rpm, Melt-kneading was performed at a discharge rate of 10 kg / hour, taken into a strand shape, cooled in a water tank, and then cut using a pelletizer to produce resin pellets (A-1P) of a fluorine-based acrylic resin.

  Further, the obtained spherical organic fine particle powder (average particle size 100 μm) of the fluorine-based acrylic resin (a-1) is dissolved in methyl isobutyl ketone and filtered through 400 mesh to obtain a 20% solid content concentration solution (A-1L). It was. The number average molecular weight measured by GPC of the obtained polymer was 210,000.

(Production Example 2) Fluorine acrylic resin (A-2)
Fluorine was produced in the same manner as in Production Example 1 except that 90 parts of 2- (perfluoroethyl) ethyl methacrylate was used instead of 90 parts of 2,2,2-trifluoroethyl methacrylate in Production Example 1. A spherical organic fine particle powder (average particle size 100 μm) of the acrylic resin (a-2) was obtained. Moreover, the spherical organic fine particle powder (average particle diameter of 100 μm) of the obtained fluorine-based acrylic resin (a-2) was dissolved in methyl isobutyl ketone to obtain a 20% solid content concentration solution (A-2L). The number average molecular weight measured by GPC of the obtained polymer was 200,000.

(Production Example 3) Fluorine acrylic resin (A-3)
Fluorine was produced in the same manner as in Production Example 1 except that 90 parts of 2- (perfluoropropyl) ethyl methacrylate was used instead of 90 parts of 2,2,2-trifluoroethyl methacrylate in Production Example 1. A spherical organic fine particle powder (average particle diameter of 100 μm) of the acrylic resin (a-3) was obtained. Further, spherical organic fine particle powder (average particle size 100 μm) of the obtained fluorine-based acrylic resin (a-3) was dissolved in methyl isobutyl ketone to obtain a 20% solid content concentration solution (A-3L). The number average molecular weight measured by GPC of the obtained polymer was 200,000.

(Production Example 4) Hydroxyl group-containing acrylic resin (B-1)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel was charged with 97 parts of methyl isobutyl ketone and 35 parts of isobutyl alcohol and heated to 105 ° C. while introducing nitrogen gas, A mixture of 33 parts of methyl methacrylate, 67 parts of hydroxyethyl methacrylate and 1.4 parts of 2,2′-azobis (2-methylbutyronitrile) was added dropwise from the dropping funnel over a period of 5 hours. Next, a mixed solution of 0.2 part of 2,2′-azobis (2-methylbutyronitrile) and 16 parts of methyl isobutyl ketone was dropped at a constant rate over 1 hour. Subsequently, the mixture was stirred at 105 ° C. for 2 hours and then cooled to 50 ° C., and 33 parts of methyl ethyl ketone was added to synthesize a polymer (B-1L). The polymer (b1-1) obtained had a solid content concentration of 35%, a number average molecular weight measured by GPC of 5600, and a solid content hydroxyl value of 285.

(Production Example 5) Hydroxyl group-containing acrylic resin (B-2)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel was charged with 97 parts of methyl isobutyl ketone and 35 parts of isobutyl alcohol and heated to 105 ° C. while introducing nitrogen gas, A mixture of 55 parts of methyl methacrylate, 45 parts of hydroxyethyl methacrylate and 0.7 part of 2,2′-azobis (2-methylbutyronitrile) was added dropwise from the dropping funnel over a period of 5 hours. Next, a mixed solution of 0.2 part of 2,2′-azobis (2-methylbutyronitrile) and 16 parts of methyl isobutyl ketone was dropped at a constant rate over 1 hour. Subsequently, the mixture was stirred at 105 ° C. for 2 hours and then cooled to 50 ° C., and 33 parts of methyl ethyl ketone was added to synthesize a polymer (B-2L). The polymer (b1-2) obtained had a solid content concentration of 35%, a number average molecular weight measured by GPC of 14,000, and a solid content hydroxyl value of 193. Moreover, the obtained hydroxyl group-containing acrylic resin (b1-2) was pulverized with a solvent in a dryer to obtain pellets (B-2P).

(Production Example 6) Hydroxyl group-containing acrylic resin (B-3)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel was charged with 97 parts of methyl isobutyl ketone and 35 parts of isobutyl alcohol and heated to 105 ° C. while introducing nitrogen gas, A mixture of 35 parts of methyl methacrylate, 20 parts of hydroxyethyl methacrylate, 45 parts of butyl methacrylate and 1.4 parts of 2,2′-azobis (2-methylbutyronitrile) was added dropwise from the dropping funnel over a period of 5 hours. Next, a mixed solution of 0.2 part of 2,2′-azobis (2-methylbutyronitrile) and 16 parts of methyl isobutyl ketone was dropped at a constant rate over 1 hour. Subsequently, the mixture was stirred at 105 ° C. for 2 hours and then cooled to 50 ° C., and 33 parts of methyl ethyl ketone was added to synthesize a polymer (B-3L). The obtained polymer (b1-3) had a solid content concentration of 35%, a number average molecular weight measured by GPC of 15000, and a solid content hydroxyl value of 85.

(Production Example 7) Acrylic resin (C-1)
<Acrylic elastic body graft copolymer (c1-1)>
The following substances were charged into an 8 L polymerization apparatus equipped with a stirrer.
・ Deionized water 200 parts ・ Sodium dioctylsulfosuccinate 0.25 parts ・ Sodium formaldehyde sulfoxylate 0.15 parts ・ Ethylenediaminetetraacetic acid-2-sodium 0.001 part ・ Ferrous sulfate 0.00025 Part

  After sufficiently replacing the inside of the polymerization apparatus with nitrogen gas to make it substantially free of oxygen, the internal temperature was adjusted to 60 ° C., 30 parts of the following monomer mixture (c1-1a) and 2- (2′-hydroxy-5) '-Methacryloyloxyethylphenyl) -2-H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., RUVA-93) was continuously added at a rate of 10 parts by weight / hour, and the addition was completed. Thereafter, the polymerization was further continued for 0.5 hours to obtain acrylate-based crosslinked elastic particles (average particle diameter d = 60 nm). The polymerization conversion rate was 99.5%.

Monomer mixture (c1-1a):
-Vinyl monomer mixture (butyl acrylate (BA) 90% and methyl methacrylate (MMA) 10%) 100 parts-allyl methacrylate (AlMA) 1 part-cumene hydroperoxide (CHP) 0.2 part

  Thereafter, 0.05 part by weight of sodium dioctylsulfosuccinate was charged, the internal temperature was adjusted to 60 ° C., 100 parts of a vinyl monomer mixture (BA 10% and MMA 90%), tartarid decyl mercaptan (t-DM) 0 70 parts of a monomer mixture (c1-1b) consisting of 0.5 part and 0.5 part of CHP was continuously added at a rate of 10 parts / hour, and the polymerization was continued for another 1 hour. A union (c1-1) (average particle size = 180 μm) was obtained. The polymerization conversion rate was 98.2%. The obtained latex was salted out and coagulated with calcium chloride, washed with water and dried to obtain a resin powder (c1-1).

<Methacrylic polymer (c1-2)>
As the methacrylic polymer (c1-2), a methyl methacrylate / methyl acrylate copolymer (Sumitomo Chemical Co., Ltd., Sumipex LG, beads) was used.

<Acrylic resin (C-1)>
After mixing 25 parts of the acrylic elastomer graft copolymer (c1-1) and 75 parts of the methacrylic polymer (c1-2) obtained as described above using a Henschel mixer, the cylinder temperature was set to 200 ° C to Using a 40mmφ single screw extruder (manufactured by Osaka Seiki Kogaku Co., Ltd.) adjusted to 260 ° C, melt kneading at a screw speed of 90rpm and a discharge rate of 15kg / hour, taking it into a strand, and cooling in a water bath Then, it cut | disconnected using the pelletizer and manufactured the resin pellet (C-1P) of acrylic resin.

(Production Example 8) Acrylic resin (C-2)
<Acrylic elastic body graft copolymer (c2-1)>
The following substances were charged into an 8 liter polymerization machine equipped with a stirrer, a thermometer, a nitrogen gas introduction pipe, a monomer supply pipe, and a reflux condenser.
・ Water (ion exchange water) 200 parts ・ Sodium formaldehyde sulfoxylate 0.15 parts ・ Ferrous sulfate ・ Dihydrate 0.0015 parts ・ Ethylenediaminetetraacetic acid-2-sodium 0.006 parts ・ Dioctylsulfosuccinic acid 0.0015 part of sodium

  After sufficiently replacing the inside of the polymerization vessel with nitrogen gas to make it substantially free of oxygen, the internal temperature was set to 60 ° C., and a vinyl monomer mixture (BA 84%, MMA 8% and styrene (ST) 8%) 100 50 parts of a monomer mixture (c2-1a) consisting of 1 part of AlMA, 1 part of AlMA and 0.1 part of CHP was continuously added at a rate of 15 parts / hour, and after completion of the addition, the polymerization was continued for another hour, Acrylic ester-based crosslinked elastic particles (average particle diameter d = 210 nm) were obtained. The polymerization conversion rate was 98.5%.

  Thereafter, 0.05 part of sodium dioctylsulfosuccinate was charged, the internal temperature was adjusted to 60 ° C., 100 parts of a vinyl monomer mixture (MMA 90% and BA 10%), t-DM 0.2 part and CHP 0.1 part. The monomer mixture (c2-1b) consisting of 50 parts was continuously added at a rate of 10 parts / hour, and the polymerization was continued for another 1 hour to obtain an acrylic elastic graft copolymer (c2-1) (average Particle size = 200 μm) was obtained. The polymerization conversion rate was 99.0%. The obtained latex was salted out and coagulated with calcium chloride, washed with water and dried to obtain a resin powder (c2-1).

<Methacrylic polymer (c2-2)>
As the methacrylic polymer (c2-2), a methyl methacrylate / methyl acrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Sumipex EX, beads) was used.

<Acrylic resin (C-2)>
25 parts of the acrylic elastomer graft copolymer (c2-1) and 75 parts of the methacrylic polymer (c2-2) obtained as described above, and 1.0 part of Tinuvin 234 (manufactured by Ciba Japan) as an ultraviolet absorber. After mixing using a Henschel mixer, acrylic resin pellets (C-2) were produced in the same manner as in Production Example 6 except that the cylinder temperature was adjusted to 240 ° C.

<Preparation of laminated film>
Example 1
Melting and kneading the resin pellets (C-2) of acrylic resin obtained in Production Example 8 at a cylinder set temperature of 180 to 240 ° C. and a discharge rate of 10 kg / hr using a 40 mmφ single screw extruder with a T-die A 75 μm thick resin film was obtained at a die temperature of 240 ° C. On the acrylic resin film, a 35% solution (B-1L) of a hydroxyl group-containing acrylic resin was No. After coating with an 8 bar coater, setting at room temperature for 10 seconds and drying with an 80 ° C. dryer for 2 minutes, the base layer resin film thickness is 4 μm, and a 20% solution (A-1L) of a fluorine-based acrylic resin is No. After coating with a 12 bar coater, the film was set for 10 seconds at room temperature, and after drying for 2 minutes with an 80 ° C. dryer, a laminated acrylic film having a film thickness of 4 μm and a total film thickness of 83 μm was obtained.

  The evaluation results regarding the obtained film are shown in Table 1.

(Example 2)
In place of (A-1L) used in Example 1, a 20% solution (A-2L) of the fluorinated acrylic resin obtained in Production Example 2 was used. A laminated film having a fluorine-based acrylic resin film thickness of 4 μm and a total film thickness of 83 μm was obtained in the same manner as in Example 1 except that coating was performed with a 12 bar coater.

  The evaluation results regarding the obtained film are shown in Table 1.

(Example 3)
In place of (A-1L) used in Example 1, except that the 20% solution (A-3L) of the containing acrylic resin obtained in Production Example 3 was used, in the same operation as in Example 1, A laminated film having a fluorine acrylic resin film thickness of 4 μm and a total film thickness of 83 μm was obtained.

  The evaluation results regarding the obtained film are shown in Table 1.

Example 4
It replaced with (B-1L) used in Example 1, and it was the same operation as Example 1 except having used the 35% solution (B-2L) of the hydroxyl-containing acrylic resin obtained by manufacture example 4. A laminated film having a hydroxyl group-containing acrylic resin film thickness of 4 μm and a total film thickness of 83 μm was obtained.

  The evaluation results regarding the obtained film are shown in Table 1.

(Example 5)
Melting and kneading the acrylic resin resin pellets (C-1) obtained in Production Example 7 at a cylinder set temperature of 180 to 240 ° C. and a discharge rate of 10 kg / hr using a 40 mmφ single screw extruder with a T-die A 75 μm thick resin film was obtained at a die temperature of 240 ° C. On the acrylic resin film, a 35% solution (B-1L) of a hydroxyl group-containing acrylic resin was No. After coating with an 8 bar coater, the film was set for 10 seconds at room temperature, dried for 2 minutes with an 80 ° C. dryer, the film thickness of the hydroxyl group-containing acrylic resin was 4 μm, and a 20% solution (A-1L) of fluorinated acrylic resin was No. After coating with a 12 bar coater, setting was performed at room temperature for 10 seconds, and after drying for 2 minutes with an 80 ° C. dryer, a laminated acrylic film having a film thickness of 4 μm and a total film thickness of 83 μm was obtained.

  The evaluation results regarding the obtained film are shown in Table 1.

(Example 6)
Resin pellets (A-2P) obtained in Production Example 1 and hydroxyl groups obtained in Production Example 5 using the acrylic resin resin pellets (C-2) obtained in Production Example 8 as the base resin. A laminated film having a total film thickness of 83 μm (a hydroxyl group-containing acrylic resin layer of 4 μm and a fluorine-based acrylic resin of 4 μm on a base layer resin of 75 μm) is formed by using the following acrylic resin (B-2P) as a surface layer resin. Obtained.

As T-die used for coextrusion, 3 types 3 layer T-die (feed block system) was used.
As an extruder on the acrylic resin side, a 40 mmφ single screw extruder is used, and melt kneading is performed at a cylinder set temperature of 200 to 260 ° C. at a discharge rate of 5 to 15 kg / hr. On the other hand, a hydroxyl group-containing acrylic resin and a fluorine-based acrylic As the extruder on the resin side, a 32 mmφ single screw extruder was used, melted and kneaded at a cylinder set temperature of 180 to 240 ° C. at a discharge rate of 0.5 to 3 kg / hr, and the die set at a die temperature of 240 ° C. Molten resin was thrown in to obtain a laminated film.

  The evaluation results regarding the obtained film are shown in Table 1.

(Comparative Example 1)
Melting and kneading the resin pellets (C-2) of the acrylic resin obtained in Production Example 8 at a cylinder set temperature of 180 to 240 ° C. and a discharge rate of 10 kg / hr using a 40 mmφ single screw extruder with a T-die A 75 μm thick resin film was obtained at a die temperature of 240 ° C.

  The evaluation results regarding the obtained film are shown in Table 1.

(Comparative Example 2)
Melting and kneading the resin pellets (C-2) of acrylic resin obtained in Production Example 8 at a cylinder set temperature of 180 to 240 ° C. and a discharge rate of 10 kg / hr using a 40 mmφ single screw extruder with a T-die A 75 μm thick resin film was obtained at a die temperature of 240 ° C. On the acrylic resin film, a 35% solution (B-1L) of a hydroxyl group-containing acrylic resin was No. After coating with an 8 bar coater, the film was set at room temperature for 10 seconds, and dried for 2 minutes with an 80 ° C. dryer to obtain a laminated film having a hydroxyl group-containing acrylic resin film thickness of 4 μm and a total film thickness of 79 μm.

  The evaluation results regarding the obtained film are shown in Table 1.

(Comparative Example 3)
Melting and kneading the resin pellets (C-2) of acrylic resin obtained in Production Example 8 at a cylinder set temperature of 180 to 240 ° C. and a discharge rate of 10 kg / hr using a 40 mmφ single screw extruder with a T-die Then, a single layer resin film having a thickness of 75 μm was obtained at a die temperature of 240 ° C. On the acrylic resin film, a 20% solution (A-1L) of a fluorine-based acrylic resin was used as No. 1 After coating with a 12 bar coater, the film was set at room temperature for 10 seconds, and after drying for 2 minutes with an 80 ° C. dryer, a laminated acrylic film having a film thickness of 4 μm and a total film thickness of 79 μm was obtained.

  The evaluation results regarding the obtained film are shown in Table 1.

(Comparative Example 4)
A laminated film having a total film thickness of 83 μm was obtained in the same manner as in Example 1 except that the 35% solution (B-3L) of the hydroxyl group-containing acrylic resin obtained in Production Example 6 was used.

  The evaluation results regarding the obtained film are shown in Table 1.

  (Comparative Example 5) Takenate D-110N (Mitsui Chemicals, Inc.), which is a urethane curing agent (b2-1), with respect to 100 parts of a 35% solution (B-1L) of a hydroxyl group-containing acrylic resin obtained in Production Example 4 A laminated film having a total film thickness of 83 μm was obtained in the same manner as in Example 1 except that a mixed solution containing 12.5 parts of polyisocyanate (NCO% = 11.5% solid content = 75%) was used. It was.

The evaluation results regarding the obtained film are shown in Table 1.

  As shown in Table 1, the laminated film of the present invention is excellent in transparency, surface hardness, chemical resistance, and stain resistance against sunscreens and insecticides that could not be realized only with a fluorine-based acrylic resin layer. I understand. In addition, the film has an excellent balance of chemical resistance, lactic acid component contained in human sebum / sweat, anti-contamination against sunscreen and insecticide, and transparency, and an optimal film for an automobile interior / exterior member can be obtained.

Claims (6)

A fluorine-based acrylic resin layer is laminated on a base film through a base layer,
Look-containing resin the base layer is solid hydroxyl value 150 or more, the resin is a hydroxyl-containing vinyl monomer, a other copolymerizable vinyl monomer copolymerized acrylic resin, the base The layer contains no hardener,
A laminated film in which the base film is made of an acrylic resin . The laminated film according to claim 1 , wherein the base film is a rubber particle-containing acrylic film. The laminated film according to claim 1 or 2 , wherein the hydroxyl group-containing vinyl monomer is a monomer represented by the general formula (1).

(In the formula, R ₁ is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, and R ₂ is H or a methyl group.) The laminate according to any one of claims 1 to 3 , wherein the fluorine-based acrylic resin layer is a layer containing an acrylic resin obtained by copolymerizing a fluorine-containing vinyl monomer and another copolymerizable vinyl monomer. the film. The laminated film according to claim 4 , wherein the fluorine-containing vinyl monomer is a monomer represented by the general formula (2).

(In the formula, R ₁ is a direct bond, straight or branched chain alkylene group having 1 to 7 carbon atoms or a fluorine-substituted alkylene group in which any of the H is substituted with F on the alkylene radical,, R ₂ is H or methyl group.) The laminated film according to any one of claims 1 to 5 , wherein the use of the laminated film is vacuum forming, pressure forming, vacuum / pressure forming, insert forming, in-mold forming.